An ink jet recording sheet comprising a sheet support, e.g., paper, bearing a surface coating comprising (a) a water soluble organic polymeric binder, (b) a titanium chelate crosslinking agent as defined, and (c) an inorganic filler, the weight ratio of (c) to (a) preferably being about 7 to 1 to about 1 to 2. The ink jet recording sheet is useful for ink jet printing.
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1. An opaque ink jet recording sheet comprising a support and a surface coating on the support, the surface coating comprising (a) a water soluble polymeric binder, (b) a titanium chelate crosslinking agent having the general formula selected from the group consisting of: ##STR5## wherein X is a functional group containing oxygen or nitrogen;
Y is alkylene of 1 to 6 carbon atoms or arylalkyl R is H, alkyl of 1 to 6 carbon atoms, or hydroxy substituted alkyl of 1 to 6 carbon atoms; and ##STR6## wherein R1, R2, or R3 can be the same or different, and are alkylene of 1 to 4 carbon atoms, and R4 is alkyl of 1 to 6 carbon atoms; and (c) an inorganic filler, the binder being crosslinked to the crosslinking agent, the surface coating being applied in a weight range of from about 1 g/M2 to about 10 g/M2 and the weight ratio of (c) to (a) being about 7:1 to about 1:2.
2. An ink jet recording element according to
Y is alkylene of 1 to 6 carbon atoms or arylalkyl; R is H, alkyl of 1 to 6 carbon atoms.
3. An ink jet recording element according to
4. An ink jet recording element according to
5. An ink jet recording element according to
7. An ink jet recording element according to
8. An ink jet recording element according to
9. An ink jet recording element according to
10. An ink jet recording element according to
11. An ink jet recording element according to
12. An ink jet recording element according to
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This invention relates to an ink jet recording sheet. More particularly, this invention relates to an ink jet recording sheet having a support coated with a coating comprising a water-soluble binder, an inorganic filler and a titanium chelate crosslinking agent.
Ink jet printing is important to the business community. Not only does improved success in this endeavor require the continuous updating and improvement of the equipment such as ink jet printers, but improvement of ink jet recording sheets for use with such equipment is important. Ink jet recording sheets generally contain a coating of a polymeric organic binder and a pigment. High resolution and high chroma are desirable properties for ink jet recording sheets. The sheets, in order to achieve these properties, have a thin receptor layer and a low binder to pigment ratio. Relatively thick coating layers tend to hide the dye color and decrease chroma. A problem with having low binder to pigment ratios is that many standard polymeric binders do not have adequate binding strength. Low binding strength results in the pigment in the coating layer dusting off the support. To date, polyvinyl alcohol crosslinked with borate has provided a good coating for ink jet recording sheets. However, the quick reaction of the borate with polyvinyl alcohol requires the coating of the borate and polyvinyl alcohol in separate layers. This in turn increases the expense of the recording sheet. Common polyvinyl alcohol crosslinking agents, e.g., amine formaldehyde condensates, require higher temperatures and longer times to develop strength than is available in standard coating machines used for coating paper.
It is desired that an improved ink jet recording sheet be prepared that provides high resolution as well as high chroma in a sheet having a thin receptor layer and a relatively low binder to filler or pigment ratio, the binder being of such strength that the pigment remains in the receptor layer without dusting off.
In accordance with this invention, there is provided an opaque ink jet recording sheet comprising a support and a surface coating on the support, the surface coating comprising (a) a water soluble polymeric binder, (b) a titanium chelate crosslinking agent having the general formula selected from the group consisting of: ##STR1## wherein
X is a functional group containing oxygen or nitrogen;
Y is alkylene of 1 to 6 carbon atoms or arylalkyl;
R is H, alkyl of 1 to 6 carbon atoms or hydroxy substituted alkyl of 1 to 6 carbon atoms; and ##STR2## wherein
R1, R2 or R3 can be the same or different, and are alkylene of 1 to 4 carbon atoms, and R4 is alkyl of 1 to 6 carbon atoms; and (c) an inorganic filler.
The ink jet recording sheet of the invention includes in its coating (a) a water soluble polymeric binder, (b) a titanium chelate crosslinking agent for crosslinking the polymeric binder, and (c) an inorganic filler, preferably with a high absorption capacity.
Water soluble polymeric binders useful in the invention are those having hydroxyl or carboxyl groups which can react with the titanium chelate crosslinking agent. Some useful binders include polyvinyl alcohol, polyvinyl alcohol copolymers such as poly(vinyl alcohol-co-vinyl acetate), hydroxypropyl cellulose, acrylic resins such as poly(methyl methacrylate/ethyl acrylate/acrylic acid), sodium alginate, water soluble phenol formaldehyde resins, carboxylated styrene butadiene polymers, carboxymethyl cellulose, hydroxyurethanes, soluble collagen, gelatin, hydrolyzed ethylene vinyl acetate polymers, and polysaccharides such as xanthan gum, gum tragacanth, locust bean gum, carrageenan, guar gum, and agur, etc. Preferred are polyvinyl alcohol or a polyvinyl alcohol copolymer, such as poly(vinyl alcohol-co-vinyl acetate) commonly known as partially hydrolyzed poly(vinyl alcohol). A preferred binder is poly(methyl methacrylate/ethyl acrylate/acrylic acid), wt. ave. mol. wt. 40,000, Acid No. 80, Tg. 53°C Weight average molecular weights can be determined by gel permeation chromatography (GPC).
Compound (b) is a titanium chelate crosslinking agent having the general formula: ##STR3## wherein
X is a functional group containing oxygen or nitrogen, e.g., ketone, ester, acid salt, etc.;
Y is alkylene of 1 to 6 carbon atoms or arylalkyl wherein aryl is 6 to 10 carbon atoms and alkyl is 1 to 6 carbon atoms;
R is hydrogen, alkyl of 1 to 6 carbon atoms, or hydroxy substituted alkyl of 1 to 6 carbon atoms; and ##STR4## wherein
R1, R2 or R3 can be the same or different, and are alkylene of 1 to 4 carbon atoms, and R4 is alkyl of 1 to 6 carbon atoms.
Suitable titanium crosslinking agents are prepared as described in Smeltz, U.S. Pat. No. 4,609,479, the pertinent disclosure of which is incorporated herein by reference.
The filler, component (c), is generally an inorganic pigment such as, for example, silica, various silicates, zeolites, calcined kaolins, diatomaceous earths, barium sulfate, aluminum hydroxides, calcium carbonate, etc.
In addition to the primary ingredients (a), (b) and (c) the coating solution can contain other additives, e.g., surfactant, humectant, UV absorber, pigment dispersant, difoamer, mold inhibitor, antioxidant, latex, dye mordant and optical brightener as are known to those having ordinary skill in the art.
The relative proportions of filler component (c) to polymeric binder (a) is about 7 to 1 to about 0.5 to 1. The ratio of filler to binder is very dependant on the type of filler used A preferred range is 5 to 1 to 3 to 1. Above about 7 to 1 there is dusting since the polymeric binder does not adequately hold the filler. At the ratio of 1 to 2, the coating surface becomes too glossy and loses its paper look.
Useful supports include cellulose and non-cellulose type supports, although the cellulose type supports, such as paper, are preferred. The degree of sizing for the support can be from 1 second to 1000 seconds as measured by the Hercules size test (HST), as described in TAPPI standards T530 pm-83. The support is chosen so its HST value is compatible with the volume and composition of the ink drop in the printer to be used. For the Iris printer, the preferred HST is in the range of 200 to 500 seconds, most preferably about 350 to 400 seconds.
The surface coating is applied to the sheet support surface in a dry coating weight range of about 10 g/M2 to about 2 g/M2. At a dry coating weight of less than about 2 g/M2 the ink spread is too great upon printing, e.g., using a Herts Iris 3024 ink jet printer manufactured by Iris Graphics, Inc., Bedford, Mass. At a coating weight of more than 10 g/M2, low chroma is attained because the dye is hidden by the quantity of filler. Chroma is lost by increased light scattering.
The surface coating is applied to the sheet support by coating means known to those skilled in the art. Suitable coating methods include: conventional roller coating or knife coating methods, e.g., air knife, trailing blade, etc. All the ingredients can be premixed to form the coating that is applied to the surface of the sheet support at the dry coating weights set out above. It is entirely unexpected that the crosslinking agent can be present with the polymeric binder for an extended period of time prior to coating, e.g., 24 hours. Boron-type crosslinking agents, for example, borate, well known as useful for crosslinking polyvinyl alcohol, etc., must be put on in a separate layer because they crosslink a binder such as polyvinyl alcohol instantly. The titanium chelates used in the present invention, as noted, can be present with the polymeric binders over extended periods of time. It is desirable, however, to not hold the coating solution at a temperature above about 50°C for too long a time.
The coating solution of the invention can be coated onto the sheet support from a single solution. The coating solution has a relatively low binder to filler ratio and upon drying on the sheet support exhibits little, if any, dusting off of the filler. The ink jet recording sheet has high resolution and high chroma. It provides an excellent ink jet printing surface.
The following examples, wherein the percentages and parts are by weight, illustrate but do not limit the invention. The printer described in the examples is a Herts, continuous drop ink jet printer. Ink is pumped through a vibrating capillary tube at high pressure. The ink stream breaks up into uniform droplets. Nonimage drops are charged and are electrically deflected into a gutter. Image droplets land on a paper which is carried past the droplet stream, usually by mounting the paper on a revolving drum.
19.7 Kg of polyvinyl alcohol (pVOH), having a viscosity of 28 to 32 as a 4% solution and a mole percent degree of hydrolysis of 99.0 to 99.8, were added to the vortex of 585 Kg of rapidly stirred deionized water. This mixture was stirred for 10 minutes at room temperature. The pVOH was dissolved by heating the mixture to 95°C for 30 minutes. 99 Kg of 4 μm silica, Syloid® 72, Davison Chemical Division, W. R. Grace & Co., Baltimore, Md., was added and the mixture was stirred with high shear for 15 minutes. After the mixture cooled to room temperature, 25 Kg of Tyzor® 101 Organic Titanate, E. I. du Pont de Nemours and Company, Wilmington, Del., was added. This gave 712 Kg of slurry which had a viscosity of 100 cps and measured 17 percent solids. This slurry was coated on an 80 g/M2, 350 HST paper stock, Schoeller Technical Papers, Inc., Pulaski, N.Y., at 300 ft/min (60.96 M/min) at the rate of 4 g/M2. The coating was dried to final moisture of six percent and had good adhesion to the paper stock and showed no dusting when rubbed by hand.
A 16.5% slurry of Syloid® 72 silica described in Example 1 was prepared by mixing with high shear 33 g of the silica and 167 g of deionized water in a Waring blender for 15 minutes. To 150 g of 4% pVOH solution was added 7.5 g of Tyzor® 101 described in Example 1. These two were mixed in the proportions shown in Table 1 below to give the pigment to binder ratios shown. The resulting slurries were coated on an 80 g/M2 350 HST paper stock described in Example 1 at a coating weight of approximately 5 g/M2 and were dried at 50°C for 10 minutes. As can be seen in Table 1, if the pigment to binder ratio was greater than 7 to 1, the coating showed dusting.
| TABLE 1 |
| ______________________________________ |
| Pigment/Binder |
| 16.5% Silica |
| 4% pVOH Ratio Dusting |
| ______________________________________ |
| 18.2 15 5/1 no |
| 18.2 13.6 5.5/1 no |
| 18.2 12.5 6/1 no |
| 18.2 11.5 6.5/1 no |
| 18.2 10.7 7/1 no |
| 18.2 10.0 7.5/1 slight |
| 18.2 9.4 8/1 yes |
| 18.2 8.3 9/1 yes |
| 18.2 7.5 10/1 yes |
| ______________________________________ |
A 16.5% silica slurry and a 4% pVOH solution were prepared as described in Example 2. These were combined as shown in Table 2 below to give decreasing pigment to binder (P/B) ratios. The combined components were coated and dried as described in Example 2. The samples were evaluated for appearance and were printed on an Iris 3024 ink jet printer with a six color test target. As shown in Table 2, as the P/B drops below 1 to 2, the surface looks glossy and no longer has the appearance of normal paper. Table 2 also shows that the average chroma dropped as the P/B decreased.
| TABLE 2 |
| ______________________________________ |
| Average |
| P/B 16.5% Silica |
| 4% pVOH Glossy |
| Chroma* |
| ______________________________________ |
| 1/1 6 25 no 65.23 |
| 1/2 3 25 no 61.35 |
| 1/3 3 25 slightly |
| 60.33 |
| 1/6 1 25 yes 60.18 |
| 1/12 0.5 25 yes 60.01 |
| ______________________________________ |
| *Average Chroma is sum of Chroma for yellow, magenta, cyan, red, green an |
| blue divided by 6. |
A coating slurry was prepared by mixing 180 g of a 16.7% silica slurry, 150 g of a 4% pVOH solution, and 7.5 g of Tyzor® 101 described in Example 1. This slurry was coated onto an 80 g/M2 350 HST paper stock as described in Example 1 at the coating weights shown in Table 3. The coatings were dried at 50°C for 5 minutes. A six color test pattern was printed onto the paper using an Iris 3024 ink jet printer described in Example 3. As seen in Table 3, the optimum coating weight is in the range of 1 to 6 g/M2.
| TABLE 3 |
| ______________________________________ |
| gms/M2 Average Chroma* |
| ______________________________________ |
| 16.5 63.0 |
| 11.5 64.0 |
| 8.6 65.2 |
| 6.0 68.8 |
| 3.0 72.0 |
| 1.25 69.5 |
| 0.53 64.1 |
| 0.47 63.7 |
| ______________________________________ |
| *See Table 2 |
180 g of a 16.7% silica slurry and 150 g of 4% pVOH were mixed. To 33 g portions of this mixture was added the amounts of Tyzor® 101 described in Example 1 as shown in Table 4. The portion was then coated at approximately 3 g/M2 and dried 5 minutes at 50°C As can be seen in Table 4 below, at least 1.25 g of titanium chelate is needed for each 1.0 g of pVOH. At lower levels, the amount of pVOH crosslinking is not sufficient to strengthen the coating against abrasion.
| TABLE 4 |
| ______________________________________ |
| Titanium Chelate |
| g/g PVOH Dusting |
| ______________________________________ |
| 0 yes |
| 0.42 yes |
| 0.83 slight |
| 1.25 no |
| 1.67 no |
| 2.50 no |
| 4.17 no |
| ______________________________________ |
180 g of a 16.7% silica dispersion, 150 g of 4% pVOH and 7.5 g of Tyzor® 101 were mixed together and the viscosity was measured to be 13 cps. After this slurry was stirred at room temperature for 18 hours, the viscosity was measured again and found to be 12 cps. The viscosity did not change, within the experimental measurement error. Coatings were made on a paper with the fresh and the aged slurry. Both showed no dusting. The paper used had an underlayer coating of 4 g/M2 clay.
40 g of a 16.7% slurry of a 4 μm silica was prepared in a 0.25% solution of the surfactant Du Pont Product BCO, E. I. du Pont de Nemours and Company, Wilmington, Del. To the slurry was added 200 g of a 5% hydroxypropyl cellulose (Aqualon Klucel® Type L), and 3 g of Tyzor® TE Organic Titanate, E. I. du Pont de Nemours and Company, Wilmington, Del. This was coated at 3 g/M2 on an 80 g/M2 350 HST paper stock described in Example 1 and dried 10 minutes at 50°C The coating showed no dusting. The control coating without the organic titanate showed dusting. The sample was printed on the Iris 3024 ink jet printer described in Example 3. The chroma values were: yellow 90.4, magenta 65.4, cyan 52.2, red 2.4, green 63.5, and blue 54.4.
A 6% solution of poly(methyl methacrylate/ethyl acrylate/acrylic acid), wt. ave. mol. wt. 200,000, Acid No. 80, Tg. 37°C, was prepared by stirring 12 g of the resin, 12 g of 12N ammonium hydroxide, and 176 g of deionized water. To 10 g of the so prepared 6% solution was added 6 g of a 16.7% silica dispersion and 1.2 g of Tyzor® TE Organic Titanate described in Example 7. This was coated at 3 g/M2 on an 80 g/M2 350 HST paper stock described in Example 1 and dried 10 minutes at 50°C The coating showed no dusting. The control coating without the organic titanate showed dusting. The sample was printed on the Iris 3024 ink jet printer described in Example 3. The chroma values were yellow 94.5, magenta 67.9, cyan 54.0, red 69.5, green 64.2, and blue 57.8.
20 g of a 2.5% solution of Kelgin® XL (sodium alginate), Kelco Division of Merck & Co., Inc., San Diego, Calif., were added to 3 g of a 16.7% silica dispersion. 1 g of Tyzor® TE Organic Titanate described in Example 7 was added. This slurry was coated at 5 g/M2 on an 80 g/M2 350 HST paper stock described in Example 1 and dried 10 minutes at 50°C The coating showed no dusting. The control coating without the organic titanate showed dusting. The sample was printed on the Iris 3024 ink jet printer described in Example 3. The chroma values were yellow 91.5, magenta 64.8, cyan 50.4, red 67.6, green 61.3, and blue 48∅
The composition of each coating slurry is shown in Table 5 below. These were coated at 6 g/M2 on a 120 g/M2, gelatin subbed paper stock which is normally used for silver halide photographic emulsions. The samples were dried at 50°C for 5 minutes. All samples were printed on the Iris 3024 ink jet printer described in Example 3 and evaluated for average chroma. As can be seen, the other fillers give nearly equivalent chroma.
| TABLE 5 |
| ______________________________________ |
| Coating A B C D |
| ______________________________________ |
| 4% pVOH, 15 15 15 15 |
| Polyvinyl Alcohol |
| Tyzor ® 101 0.6 0.6 0.6 0.6 |
| Organic Titanate |
| 16.7% Syloid ® 72 |
| 18 12.6 12.6 12.6 |
| Silica |
| 16.7% Huberfill ® 96 |
| 0 5.0 0 0 |
| Sodium, Magnesium |
| Aluminosilicate, |
| J. M. Huber Corp., |
| Havre de Grace, MD |
| 16.7% Paperadd ® PGAB 741 |
| 0 0 5.4 0 |
| Hydrated Alumia, |
| Reynolds Metals Co., |
| Richmond, VA |
| 16.7% Atomite ® |
| 0 0 0 5.4 |
| (calcium carbonate) |
| C. C. America, Inc., |
| Sylacauga, AL |
| Average chroma 64.4 62.2 62.6 62.7 |
| ______________________________________ |
Two slurries were prepared wherein both were composed of 18 g of 16.7% silica slurry and 15 g of 4% pVOH. To one was added 1 g of a 5% sodium borate solution and to the other was added 1 g of a 5% boric acid solution. Both slurries quickly contain large clumps of gelled material and were not coatable.
| Patent | Priority | Assignee | Title |
| 5385764, | Aug 11 1992 | E KHASHOGGI INDUSTRIES, LLC | Hydraulically settable containers and other articles for storing, dispensing, and packaging food and beverages and methods for their manufacture |
| 5429860, | Feb 28 1994 | E I DU PONT DE NEMOURS AND COMPANY | Reactive media-ink system for ink jet printing |
| 5453310, | Aug 11 1992 | E KHASHOGGI INDUSTRIES, LLC | Cementitious materials for use in packaging containers and their methods of manufacture |
| 5508072, | Aug 11 1992 | E KHASHOGGI INDUSTRIES, LLC | Sheets having a highly inorganically filled organic polymer matrix |
| 5514430, | Aug 11 1992 | E KHASHOGGI INDUSTRIES, LLC | Coated hydraulically settable containers and other articles for storing, dispensing, and packaging food and beverages |
| 5523149, | Jul 14 1993 | Mitsubishi Paper Mills Limited | Alumina sol coated recording sheet |
| 5537137, | Feb 28 1994 | E. I. du Pont de Nemours and Company | Reactive media-ink system for ink jet printing |
| 5545450, | Aug 11 1992 | E KHASHOGGI INDUSTRIES, LLC | Molded articles having an inorganically filled organic polymer matrix |
| 5580624, | Aug 11 1992 | EARTHSHELL SPE, LLC | Food and beverage containers made from inorganic aggregates and polysaccharide, protein, or synthetic organic binders, and the methods of manufacturing such containers |
| 5582670, | Nov 25 1992 | E KHASHOGGI INDUSTRIES, LLC | Methods for the manufacture of sheets having a highly inorganically filled organic polymer matrix |
| 5616443, | Feb 22 1995 | Kimberly-Clark Worldwide, Inc | Substrate having a mutable colored composition thereon |
| 5618341, | Aug 11 1992 | E KHASHOGGI INDUSTRIES, LLC | Methods for uniformly dispersing fibers within starch-based compositions |
| 5631052, | Aug 12 1992 | E KHASHOGGI INDUSTRIES, LLC | Coated cementitious packaging containers |
| 5631053, | Aug 11 1992 | E KHASHOGGI INDUSTRIES, LLC | Hinged articles having an inorganically filled matrix |
| 5641584, | Aug 11 1992 | E KHASHOGGI INDUSTRIES, LLC | Highly insulative cementitious matrices and methods for their manufacture |
| 5643356, | Aug 05 1993 | Kimberly-Clark Worldwide, Inc | Ink for ink jet printers |
| 5643701, | Feb 22 1995 | Kimberly-Clark Worldwide, Inc | Electrophotgraphic process utilizing mutable colored composition |
| 5645964, | Aug 05 1993 | Kimberly-Clark Worldwide, Inc | Digital information recording media and method of using same |
| 5654048, | Aug 11 1992 | E KHASHOGGI INDUSTRIES, LLC | Cementitious packaging containers |
| 5658603, | Aug 11 1992 | EARTHSHELL SPE, LLC | Systems for molding articles having an inorganically filled organic polymer matrix |
| 5660900, | Aug 11 1992 | EARTHSHELL SPE, LLC | Inorganically filled, starch-bound compositions for manufacturing containers and other articles having a thermodynamically controlled cellular matrix |
| 5660903, | Aug 11 1992 | E KHASHOGGI INDUSTRIES, LLC | Sheets having a highly inorganically filled organic polymer matrix |
| 5660904, | Aug 11 1992 | E KHASHOGGI INDUSTRIES, LLC | Sheets having a highly inorganically filled organic polymer matrix |
| 5662731, | Aug 11 1992 | EARTHSHELL SPE, LLC | Compositions for manufacturing fiber-reinforced, starch-bound articles having a foamed cellular matrix |
| 5665442, | Nov 25 1992 | E KHASHOGGI INDUSTRIES, LLC | Laminated sheets having a highly inorganically filled organic polymer matrix |
| 5679145, | Aug 11 1992 | E KHASHOGGI INDUSTRIES, LLC | Starch-based compositions having uniformly dispersed fibers used to manufacture high strength articles having a fiber-reinforced, starch-bound cellular matrix |
| 5681380, | Jun 05 1995 | Kimberly-Clark Worldwide, Inc. | Ink for ink jet printers |
| 5683772, | Aug 11 1992 | EARTHSHELL SPE, LLC | Articles having a starch-bound cellular matrix reinforced with uniformly dispersed fibers |
| 5683843, | Aug 05 1993 | Kimberly-Clark Worldwide, Inc | Solid colored composition mutable by ultraviolet radiation |
| 5688603, | Oct 26 1995 | Minnesota Mining and Manufacturing Company | Ink-jet recording sheet |
| 5691014, | Aug 11 1992 | E KHASHOGGI INDUSTRIES, LLC | Coated articles having an inorganically filled organic polymer matrix |
| 5700850, | Aug 05 1993 | Kimberly-Clark Worldwide, Inc | Colorant compositions and colorant stabilizers |
| 5702787, | Aug 11 1992 | E KHASHOGGI INDUSTRIES, LLC | Molded articles having an inorganically filled oragnic polymer matrix |
| 5705237, | Aug 11 1992 | E KHASHOGGI INDUSTRIES, LLC | Hydraulically settable containers and other articles for storing, dispensing, and packaging food or beverages |
| 5705238, | Aug 11 1992 | E KHASHOGGI INDUSTRIES, LLC | Articles of manufacture fashioned from sheets having a highly inorganically filled organic polymer matrix |
| 5705239, | Aug 11 1992 | EARTHSHELL SPE, LLC | Molded articles having an inorganically filled organic polymer matrix |
| 5705242, | Aug 11 1992 | E KHASHOGGI INDUSTRIES, LLC | Coated food beverage containers made from inorganic aggregates and polysaccharide, protein, or synthetic organic binders |
| 5707474, | Aug 11 1992 | E KHASHOGGI INDUSTRIES, LLC | Methods for manufacturing hinges having a highly inorganically filled matrix |
| 5707722, | Oct 26 1995 | Minnesota Mining and Manufacturing Company | Ink jet recording sheet |
| 5709827, | Aug 11 1992 | EARTHSHELL SPE, LLC | Methods for manufacturing articles having a starch-bound cellular matrix |
| 5709913, | Aug 11 1992 | E KHASHOGGI INDUSTRIES, LLC | Method and apparatus for manufacturing articles of manufacture from sheets having a highly inorganically filled organic polymer matrix |
| 5709955, | Jun 30 1994 | Kimberly-Clark Worldwide, Inc | Adhesive composition curable upon exposure to radiation and applications therefor |
| 5721287, | Aug 05 1993 | Kimberly-Clark Worldwide, Inc | Method of mutating a colorant by irradiation |
| 5733693, | Aug 05 1993 | Kimberly-Clark Worldwide, Inc. | Method for improving the readability of data processing forms |
| 5738921, | Aug 10 1993 | E KHASHOGGI INDUSTRIES, LLC | Compositions and methods for manufacturing sealable, liquid-tight containers comprising an inorganically filled matrix |
| 5739175, | Jun 05 1995 | Kimberly-Clark Worldwide, Inc | Photoreactor composition containing an arylketoalkene wavelength-specific sensitizer |
| 5747550, | Jun 05 1995 | Kimberly-Clark Worldwide, Inc | Method of generating a reactive species and polymerizing an unsaturated polymerizable material |
| 5753308, | Aug 11 1992 | EARTHSHELL SPE, LLC | Methods for manufacturing food and beverage containers from inorganic aggregates and polysaccharide, protein, or synthetic organic binders |
| 5773182, | Aug 05 1993 | Kimberly-Clark Worldwide, Inc | Method of light stabilizing a colorant |
| 5782963, | Mar 29 1996 | Kimberly-Clark Worldwide, Inc | Colorant stabilizers |
| 5783126, | Aug 11 1992 | EARTHSHELL SPE, LLC | Method for manufacturing articles having inorganically filled, starch-bound cellular matrix |
| 5786132, | Jun 05 1995 | Kimberly-Clark Worldwide, Inc | Pre-dyes, mutable dye compositions, and methods of developing a color |
| 5798015, | Jun 05 1995 | Kimberly-Clark Worldwide, Inc | Method of laminating a structure with adhesive containing a photoreactor composition |
| 5800647, | Aug 11 1992 | E KHASHOGGI INDUSTRIES, LLC | Methods for manufacturing articles from sheets having a highly inorganically filled organic polymer matrix |
| 5811199, | Jun 05 1995 | Kimberly-Clark Worldwide, Inc | Adhesive compositions containing a photoreactor composition |
| 5830305, | Aug 11 1992 | EARTHSHELL SPE, LLC | Methods of molding articles having an inorganically filled organic polymer matrix |
| 5830548, | Aug 11 1992 | E KHASHOGGI INDUSTRIES, LLC | Articles of manufacture and methods for manufacturing laminate structures including inorganically filled sheets |
| 5837429, | Jun 05 1995 | Kimberly-Clark Worldwide, Inc | Pre-dyes, pre-dye compositions, and methods of developing a color |
| 5849155, | Feb 02 1993 | E KHASHOGGI INDUSTRIES, LLC | Method for dispersing cellulose based fibers in water |
| 5849411, | Jun 05 1995 | Kimberly-Clark Worldwide, Inc | Polymer film, nonwoven web and fibers containing a photoreactor composition |
| 5851634, | Aug 11 1992 | E KHASHOGGI INDUSTRIES, LLC | Hinges for highly inorganically filled composite materials |
| 5855655, | Mar 29 1996 | Kimberly-Clark Worldwide, Inc | Colorant stabilizers |
| 5858586, | Aug 05 1993 | Kimberly-Clark Corporation | Digital information recording media and method of using same |
| 5865471, | Aug 05 1993 | Kimberly-Clark Worldwide, Inc | Photo-erasable data processing forms |
| 5866268, | Sep 13 1995 | Arkwright, Incorporated | Liquid sorptive coating for ink jet recording media |
| 5879722, | Aug 11 1992 | E KHASHOGGI INDUSTRIES, LLC | System for manufacturing sheets from hydraulically settable compositions |
| 5885337, | Jan 22 1996 | Colorant stabilizers | |
| 5891229, | Mar 29 1996 | Kimberly-Clark Worldwide, Inc | Colorant stabilizers |
| 5908495, | Aug 05 1993 | Ink for ink jet printers | |
| 5916673, | Apr 19 1994 | Ilford Imaging Switzerland GmbH | Recording sheets for ink jet printing |
| 5928741, | Aug 11 1992 | E KHASHOGGI INDUSTRIES, LLC | Laminated articles of manufacture fashioned from sheets having a highly inorganically filled organic polymer matrix |
| 5932355, | Feb 07 1997 | Minnesota Mining and Manufacturing Company | Ink-jet recording sheet |
| 6008268, | Jun 30 1994 | Kimberly-Clark Worldwide, Inc. | Photoreactor composition, method of generating a reactive species, and applications therefor |
| 6017471, | Aug 05 1993 | Kimberly-Clark Worldwide, Inc. | Colorants and colorant modifiers |
| 6017661, | Aug 05 1993 | Kimberly-Clark Corporation | Temporary marking using photoerasable colorants |
| 6030673, | Nov 25 1992 | EARTHSHELL SPE, LLC | Molded starch-bound containers and other articles having natural and/or synthetic polymer coatings |
| 6033465, | Jun 28 1995 | Kimberly-Clark Worldwide, Inc.; Kimberly-Clark Worldwide, Inc | Colorants and colorant modifiers |
| 6037050, | Oct 25 1996 | Konica Corporation | Ink-jet recording sheet |
| 6051306, | Nov 15 1996 | FARGO ELECTRONICS, INC | Ink jet printable surface |
| 6054256, | Aug 05 1993 | Kimberly-Clark Worldwide, Inc. | Method and apparatus for indicating ultraviolet light exposure |
| 6060200, | Aug 05 1993 | Kimberly-Clark Worldwide, Inc. | Photo-erasable data processing forms and methods |
| 6060223, | Aug 05 1993 | Kimberly-Clark Worldwide, Inc. | Plastic article for colored printing and method for printing on a colored plastic article |
| 6063551, | Jun 15 1995 | Kimberly-Clark Worldwide, Inc. | Mutable dye composition and method of developing a color |
| 6066439, | Aug 05 1993 | Kimberly-Clark Worldwide, Inc. | Instrument for photoerasable marking |
| 6071979, | Jun 30 1994 | Kimberly-Clark Worldwide, Inc. | Photoreactor composition method of generating a reactive species and applications therefor |
| 6090236, | Jun 30 1994 | Kimberly-Clark Worldwide, Inc. | Photocuring, articles made by photocuring, and compositions for use in photocuring |
| 6099628, | Nov 27 1996 | Kimberly-Clark Worldwide, Inc | Colorant stabilizers |
| 6114022, | Aug 11 1997 | 3M Innovative Properties Company | Coated microporous inkjet receptive media and method for controlling dot diameter |
| 6120949, | Aug 05 1993 | Kimberly-Clark Worldwide, Inc. | Photoerasable paint and method for using photoerasable paint |
| 6127073, | Aug 05 1993 | Kimberly-Clark Worldwide, Inc. | Method for concealing information and document for securely communicating concealed information |
| 6168654, | Mar 29 1996 | Kimberly-Clark Worldwide, Inc | Colorant stabilizers |
| 6168655, | Jan 22 1996 | Kimberly-Clark Worldwide, Inc. | Colorant stabilizers |
| 6211383, | Aug 05 1993 | Kimberly-Clark Worldwide, Inc. | Nohr-McDonald elimination reaction |
| 6217166, | Jul 01 1997 | Konica Corporation | Ink jet recording method |
| 6228157, | Jul 20 1998 | HANGER SOLUTIONS, LLC | Ink jet ink compositions |
| 6235095, | Dec 20 1994 | Ink for inkjet printers | |
| 6242057, | Jun 30 1994 | Kimberly-Clark Worldwide, Inc | Photoreactor composition and applications therefor |
| 6265458, | Sep 28 1999 | TAMIRAS PER PTE LTD , LLC | Photoinitiators and applications therefor |
| 6270858, | Nov 15 1996 | FARGO ELECTRONICS, INC | Method of coating using an ink jet printable mixture |
| 6277897, | Jun 03 1998 | Kimberly-Clark Worldwide, Inc | Photoinitiators and applications therefor |
| 6294698, | Apr 16 1999 | Kimberly-Clark Corporation; Kimberly-Clark Worldwide, Inc | Photoinitiators and applications therefor |
| 6331056, | Feb 25 1999 | Kimberly-Clark Worldwide, Inc | Printing apparatus and applications therefor |
| 6342305, | Sep 10 1993 | Kimberly-Clark Corporation | Colorants and colorant modifiers |
| 6359040, | May 12 1998 | HERCULES LLC | Aqueous systems comprising an ionic polymer and a viscosity promoter, processes for their preparation, and uses thereof |
| 6368395, | May 24 1999 | Kimberly-Clark Worldwide, Inc | Subphthalocyanine colorants, ink compositions, and method of making the same |
| 6368396, | Jan 19 1999 | Kimberly-Clark Worldwide, Inc | Colorants, colorant stabilizers, ink compositions, and improved methods of making the same |
| 6386699, | Apr 29 1998 | 3M Innovative Properties Company | Embossed receptor media |
| 6419987, | Dec 17 1999 | Eastman Kodak Company | Method for providing a high viscosity coating on a moving web and articles made thereby |
| 6503559, | Jun 03 1998 | HANGER SOLUTIONS, LLC | Neonanoplasts and microemulsion technology for inks and ink jet printing |
| 6506478, | Jun 09 2000 | 3M Innovative Properties Company | Inkjet printable media |
| 6521325, | Jun 01 1999 | 3M Innovative Properties Company | Optically transmissive microembossed receptor media |
| 6524379, | Jan 12 2000 | Kimberly-Clark Worldwide, Inc | Colorants, colorant stabilizers, ink compositions, and improved methods of making the same |
| 6555213, | Jun 09 2000 | 3M Innovative Properties Company | Polypropylene card construction |
| 6648533, | Jun 29 2001 | HEWLETT-PACKARD DEVELOPMENT COMPANY, L P | Label-making inkjet printer |
| 6649249, | Jun 01 1999 | 3M Innovative Properties Company | Random microembossed receptor media |
| 6652928, | Jan 28 1998 | Canon Kabushiki Kaisha | Image-transfer medium for ink-jet printing, production process of transferred image, and cloth with transferred image formed thereon |
| 6670002, | May 26 1998 | Mitsubishi Paper Mills Limited | Ink jet recording sheet and method for producing it |
| 6689433, | May 06 2002 | HEWLETT-PACKARD DEVELOPMENT COMPANY, L P | Print media products for generating high quality images and methods for making the same |
| 6692799, | Jun 09 2000 | Materials and methods for creating waterproof, durable aqueous inkjet receptive media | |
| 6825279, | Jun 09 2000 | 3M Innovative Properties Company | Inkjet printable media |
| 6844035, | May 06 2002 | Hewlett-Packard Development Company, L.P. | Print media products for generating high quality images and methods for making the same |
| 6848779, | Jun 29 2001 | HEWLETT-PACKARD DEVELOPMENT COMPANY, L P | Label-making inkjet printer |
| 6905742, | Jun 09 2000 | 3M Innovative Properties Company | Polypropylene card construction |
| 6913722, | Jun 01 1999 | 3M Innovative Properties Company | Method of making an optically transparent inkjet printing medium |
| 6933024, | Jul 18 2002 | HEWLETT-PACKARD DEVELOPMENT COMPANY, L P | Water soluble polymers as inkjet recording materials |
| 6979141, | Mar 05 2001 | ASSA ABLOY AB | Identification cards, protective coatings, films, and methods for forming the same |
| 6979480, | Jun 09 2000 | 3M Innovative Properties Company | Porous inkjet receptor media |
| 7037013, | Mar 05 2001 | ASSA ABLOY AB | Ink-receptive card substrate |
| 7097298, | May 17 2000 | DUPONT ELECTRONICS, INC | Ink receptor sheet and it's process of use |
| 7112629, | Feb 09 2004 | Hewlett-Packard Development Company, L.P. | Print media products for generating high quality images and methods for making the same |
| 7217447, | Jan 22 2002 | FUJIFILM Corporation | Ink-jet recording sheet |
| 7399131, | Mar 05 2001 | ASSA ABLOY AB | Method and Device for forming an ink-receptive card substrate |
| 7661806, | Mar 11 2005 | Eastman Kodak Company | Fusible reactive media comprising crosslinker-containing layer |
| 7939138, | Jun 01 2009 | POLYMER VENTURES, INC | Grease resistant coatings, articles and methods |
| 7972526, | Jun 01 2009 | Polymer Ventures, Inc. | Grease resistant coatings, articles and methods |
| 8273435, | Jun 01 2009 | POLYMER VENTURES, INC | Polyol coatings, articles, and methods |
| 8287974, | Jun 01 2009 | Polymer Ventures, Inc. | Polyol-based release paper, articles, and methods |
| 8956490, | Jun 25 2007 | ASSA ABLOY AB | Identification card substrate surface protection using a laminated coating |
| 9597913, | Nov 26 2010 | AGFA-GEVAERT NV | Image receiving material for offset printing |
| RE39339, | Aug 11 1992 | EARTHSHELL SPE, LLC | Compositions for manufacturing fiber-reinforced, starch-bound articles having a foamed cellular matrix |
| Patent | Priority | Assignee | Title |
| 4113757, | Mar 13 1976 | Tioxide Group Limited | Titanium compounds |
| 4146669, | Jan 12 1977 | Tsentralny Nauchno-Issledovatelsky Institut Bumagi (TSNIIB) | Crosslinking agent, method of producing same and paper made with the use thereof |
| 4592951, | Jul 18 1984 | POLAROID CORPORATION FMR OEP IMAGING OPERATING CORP | Ink jet recording sheet |
| 4877686, | May 20 1986 | Societe Anonyme: Aussedat-Rey | Recording sheet for ink-jet printing and process for its preparation |
| 4894279, | May 09 1986 | IBM INFORMATION PRODUCTS CORPORATION, 55 RAILROAD AVENUE, GREENWICH, CT 06830 A CORP OF DE | Electroerosion print media having protective coatings modified with organotitanium reagents |
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| Jul 15 1991 | WHEELER, JAMES W | E I DU PONT DE NEMOURS AND COMPANY | ASSIGNMENT OF ASSIGNORS INTEREST | 005782 | /0152 |
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